WO2015146733A1 - Film poreux étiré de polyéthylène de poids moléculaire ultra-élevé - Google Patents

Film poreux étiré de polyéthylène de poids moléculaire ultra-élevé Download PDF

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WO2015146733A1
WO2015146733A1 PCT/JP2015/058003 JP2015058003W WO2015146733A1 WO 2015146733 A1 WO2015146733 A1 WO 2015146733A1 JP 2015058003 W JP2015058003 W JP 2015058003W WO 2015146733 A1 WO2015146733 A1 WO 2015146733A1
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Prior art keywords
molecular weight
weight polyethylene
high molecular
ultrahigh molecular
microporous membrane
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PCT/JP2015/058003
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English (en)
Japanese (ja)
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稲富敬
若林保武
阿部成彦
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東ソー株式会社
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Priority to US15/128,772 priority Critical patent/US10340492B2/en
Priority to CN201580016422.0A priority patent/CN106133042B/zh
Priority to KR1020167025631A priority patent/KR102330629B1/ko
Publication of WO2015146733A1 publication Critical patent/WO2015146733A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/261—Polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/494—Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2325/24—Mechanical properties, e.g. strength
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
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    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a stretched microporous membrane made of ultrahigh molecular weight polyethylene having a high melting point and strength and capable of being thinned, preferably a stretched microporous membrane formed by molding ultrahigh molecular weight polyethylene particles having a high melting point and high crystallinity. More specifically, the present invention relates to a stretched microporous membrane made of ultrahigh molecular weight polyethylene, which is expected to be applied as a permeable membrane, a separation membrane, a battery separator and the like because of its excellent strength and heat resistance.
  • the ultra high molecular weight ethylene polymer has an extremely high molecular weight corresponding to a viscosity average molecular weight (Mv) of 1 million or more, so that it has impact resistance, self-lubricity, abrasion resistance, weather resistance, chemical resistance It has excellent physical properties and dimensional stability, and has high physical properties comparable to engineering plastics. For this reason, application to applications such as lining materials, food industry line parts, machine parts, artificial joints, sporting goods, and microporous membranes has been attempted by various molding methods.
  • Mv viscosity average molecular weight
  • ultra-high molecular weight ethylene polymer has extremely low fluidity when melted due to its high molecular weight, and it can be molded by kneading extrusion like ordinary polyethylene having a molecular weight in the range of tens of thousands to about 500,000.
  • ultrahigh molecular weight polyethylene is a method of directly sintering polymer powder obtained by polymerization, a method of compression molding, a molding method by a ram extruder that extrudes while intermittently compressing, a state where it is dispersed in a solvent, etc. After extrusion molding, a method such as a method of removing the solvent is performed.
  • the ultrahigh molecular weight polyethylene microporous membrane is expected to have excellent physical properties such as heat resistance, strength, and impact resistance due to the high molecular weight of ultra high molecular weight polyethylene.
  • the ultra-high molecular weight polyethylene produced by the Ziegler catalyst currently on the market has a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (molecular weight distribution) larger than 4, and the molecular weight distribution is wide.
  • Mw weight average molecular weight
  • Mn number average molecular weight distribution
  • an object of the present invention is to provide a stretched microporous membrane made of ultrahigh molecular weight polyethylene having excellent strength and heat resistance.
  • the inventors of the present invention preferably have a specific stretched microporous membrane using novel ultrahigh molecular weight polyethylene particles having a specific melting behavior, which has strength, heat resistance and durability.
  • the present invention has been completed by finding a microporous film having excellent properties.
  • the present invention resides in the following [1] to [15].
  • [1] It is made of ultrahigh molecular weight polyethylene having at least an intrinsic viscosity ([ ⁇ ]) of 7 dl / g or more and 60 dl / g or less, a porosity is 10% or more and 70% or less, and a breaking stress when melt stretched at 150 ° C. is 1 MPa.
  • An ultra-high molecular weight polyethylene stretched microporous membrane characterized by the above.
  • the ultrahigh molecular weight polyethylene is made of ultrahigh molecular weight polyethylene particles that satisfy at least any of the following properties (1) to (3):
  • the drawn microporous membrane made of ultrahigh molecular weight polyethylene as described.
  • Intrinsic viscosity ([ ⁇ ]) is 7 dl / g or more and 60 dl / g or less
  • the bulk density is 130 kg / m 3 or more and 700 kg / m 3 or less
  • the ultrahigh molecular weight polyethylene composition comprising at least an ultrahigh molecular weight polyethylene having an intrinsic viscosity ([ ⁇ ]) of 7 dl / g or more and 60 dl / g or less and a polyethylene having a weight average molecular weight of 800,000 or less.
  • the ultra high molecular weight polyethylene composition [ ⁇ ] is an ultra high molecular weight polyethylene composition having a ⁇ of 0.75 times or less of the ultra high molecular weight polyethylene component [ ⁇ ]. Of the endothermic peak due to melting when the temperature is raised to 230 ° C.
  • the ratio ( ⁇ H > 135 / ⁇ H whole ) of the heat of fusion ( ⁇ H > 135 ) of 135 ° C. or more to the total heat of fusion ( ⁇ H whole ) ) Is 40% or more and 80% or less, and the ⁇ H whole is 190 J / g or more, and the ultra-high molecular weight polyethylene stretched microporous membrane according to the above [5].
  • the DSC is heated from 0 ° C. to 230 ° C. at a rate of 10 ° C./min, the endothermic heat flux at that temperature is maximum in the range of 134 ° C. or lower and 140 ° C. or higher.
  • the ultra-high molecular weight polyethylene stretched microporous membrane according to any one of [8].
  • As ultra-high molecular weight polyethylene (4) a mold that is 10 ° C. to 30 ° C.
  • the ultra-high molecular weight polyethylene particles satisfying that the tensile breaking strength (TS (MPa)) of the sheet formed by cooling at a temperature satisfies the following relational expression (a) is used: [3 ] The ultra-high molecular weight polyethylene stretched microporous membrane according to any one of [9] to [9].
  • ultra-high molecular weight polyethylene (5) Ultra-high molecular weight satisfying that (5) heat-rolled sheet is melt-stretched at 150 ° C., the breaking stress (MTS (MPa)) is 1.5 MPa or more.
  • the stretched microporous membrane made of ultrahigh molecular weight polyethylene according to any one of the above [3] to [10], characterized by using molecular weight polyethylene particles.
  • the DC resistance is 10 ⁇ ⁇ m
  • a separator for an ultrahigh molecular weight polyethylene lithium ion secondary battery having a breaking stress of 1 MPa or more and a film thickness of 15 ⁇ m or less when melt stretched at 150 ° C. to 70%.
  • the stretched microporous membrane made of ultrahigh molecular weight polyethylene of the present invention is made of ultrahigh molecular weight polyethylene having at least [ ⁇ ] of 7 dl / g or more and 60 dl / g or less, with a porosity of 10% or more and 70% or less, and melting at 150 ° C.
  • the breaking stress when stretched is 1 MPa or more.
  • the ultrahigh molecular weight polyethylene constituting the ultrahigh molecular weight polyethylene stretched microporous membrane was prepared with a Ziegler-Natta catalyst, a metallocene catalyst, or the like if [ ⁇ ] was 7 dl / g or more and 60 dl / g or less.
  • any ultra high molecular weight polyethylene may be used, and it may be used as a composition with ordinary polyethylene. Among them, ultra high molecular weight polyethylene particles described later and a composition thereof are preferable.
  • [ ⁇ ] is less than 7 dl / g
  • the stretched microporous membrane is inferior in mechanical properties.
  • [ ⁇ ] exceeds 60 dl / g the fluidity at the time of molding is inferior, so that the moldability at the time of forming a stretched microporous film is inferior.
  • [ ⁇ ] is measured at 135 ° C.
  • the stretched microporous membrane made of ultrahigh molecular weight polyethylene of the present invention has a porosity of 10% to 70%, particularly preferably a porosity of 25% to 65%.
  • a porosity is less than 10%, a stretched microporous film having a large permeation resistance is obtained.
  • it exceeds 70% it becomes a stretched microporous film having low strength and rigidity, and is inferior in durability.
  • the stretched microporous membrane made of ultra high molecular weight polyethylene of the present invention has a breaking stress of 1 MPa or more when melt stretched at 150 ° C., and particularly has a heat resistance and melt elasticity of 2 MPa or more. It is preferable that When the breaking stress when melt stretched is less than 1 MPa, the heat resistance and durability at high temperatures are poor.
  • the breaking stress when melt-drawing at 150 ° C. in the present invention can be measured by, for example, a tensile test having a heating furnace. As a measurement condition, it can be measured by stretching a test piece having an initial length of 10 mm at a stretching speed of 10 to 50 mm / min.
  • the stretched microporous membrane made of ultra high molecular weight polyethylene of the present invention is particularly excellent in heat resistance and durability at high temperature, among endothermic peaks due to melting in 1st scan at DSC, Ratio of heat of fusion (hereinafter referred to as ⁇ H > 135 ) (J / g) to total heat of fusion (hereinafter referred to as ⁇ H whole ) (J / g) ( ⁇ H > 135 / ⁇ H whole ) Is preferably 40% or more.
  • the stretched microporous membrane made of ultrahigh molecular weight polyethylene of the present invention is particularly excellent in strength and can be thinned, and therefore, the tensile strength at break measured at 23 ° C. is preferably 150 MPa or more.
  • the heat shrinkage rate is preferably 2% or less because of excellent heat resistance, durability at high temperatures, and stability.
  • the tensile breaking strength in this invention can be measured with a tensile tester etc., for example.
  • the measurement conditions at that time can be measured by stretching a test piece having an initial length of 20 mm at a stretching speed of 10 to 100 mm / min.
  • the thermal contraction rate can be measured by, for example, heating a 5 cm square microporous membrane at 100 ° C. for 1 hour, allowing to cool for 24 hours, and measuring the subsequent shrinkage rate.
  • the stretched microporous membrane made of ultrahigh molecular weight polyethylene of the present invention can efficiently obtain a particularly excellent heat resistance and durability at high temperatures, so that at least (1) [ ⁇ ] is 7 dl / g or more. 60 dl / g or less, (2) Bulk density is 130 kg / m 3 or more and 700 kg / m 3 or less, (3) Tm 1 of 1st scan at the time of 1st scan by DSC, then left for 5 minutes, then 10 ° C. / The temperature is lowered to ⁇ 20 ° C.
  • the stretched microporous membrane made of ultrahigh molecular weight polyethylene of the present invention at least (1 ′) [ ⁇ ] is 15 dl / g or more and 60 dl / g or less, and (2) the bulk density is 130 kg / m 3 or more and 700 kg / m 3 or less. (3 ′) Tm 1 of 1st scan at the time of 1st scan at DSC, then left for 5 minutes, then dropped to ⁇ 20 ° C.
  • ultrahigh molecular weight polyethylene particles preferably applied to the stretched microporous membrane made of ultrahigh molecular weight polyethylene according to the present invention will be described.
  • the ultra high molecular weight polyethylene particles are those in which ultra high molecular weight polyethylene has a particle shape, and ultra high molecular weight polyethylenes belong to a category called polyethylene, for example, ultra high molecular weight ethylene homopolymers; Ultra high molecular weight ethylene-propylene copolymer, ultra high molecular weight ethylene-1-butene copolymer, ultra high molecular weight ethylene-1-hexene copolymer, ultra high molecular weight ethylene-1-octene copolymer, etc. ⁇ -olefin copolymer; and the like.
  • the ultra high molecular weight polyethylene particles have (1) [ ⁇ ] of 7 dl / g or more and 60 dl / g or less, preferably (1 ′) 15 dl / g or more and 60 dl / g or less, particularly a microporous membrane From the viewpoint of having excellent moldability and mechanical properties, it is preferably 15 dl / g or more and 50 dl / g or less.
  • the stretched microporous membrane is inferior in mechanical properties.
  • the bulk density is preferably 130 kg / m 3 or more and 700 kg / m 3 or less, and is particularly excellent in workability when a stretched microporous membrane is used, and is 200 kg / m 3 or more and 600 kg / m 3 or less. It is preferable.
  • the bulk density can be measured by a method based on, for example, JIS K6760 (1995).
  • polyethylene In general polyethylene, an ethylene homopolymer belonging to high-density polyethylene is known as a polyethylene having a high melting point. However, the melting point of the high density polyethylene is as low as about 130 to 135 ° C.
  • the ultra-high molecular weight polyethylene particles suitable for the stretched microporous membrane of the present invention have an extremely high melting point (Tm) as compared with conventionally known polyethylene, for example, an ethylene homopolymer. If there is, it has a very high melting point exceeding 140 ° C. as Tm 1 .
  • the ultra high molecular weight polyethylene particles are highly crystallized due to the orientation of the molecular chains of polyethylene and the like, and ⁇ Tm, which is the difference between Tm 1 and Tm 2 when measured by DSC, is 9 ° C. or more and 30 I think that it will be a very big difference of below °C.
  • the ultra high molecular weight polyethylene particles can suppress discoloration (yellowing) caused by titanium, oxidation deterioration, and the like, have a good color tone, and have excellent weather resistance. Since it becomes possible to provide a film, it is preferable that the titanium content is low, and in particular, the titanium content is preferably 0.02 ppm or less or the detection limit or less.
  • the titanium content can be determined by chemical titration, measurement using a fluorescent X-ray analyzer, ICP emission analyzer, or the like.
  • the ultrahigh molecular weight polyethylene particles can provide a tougher ultrahigh molecular weight polyethylene stretched microporous membrane, (4) after heating and compressing at a press temperature of 190 ° C. and a press pressure of 20 MPa,
  • the tensile breaking strength (TS (MPa)) of the sheet formed by cooling at a mold temperature 10 ° C. to 30 ° C. lower than Tm 2 of the 2nd scan measured in 3) satisfies the following relational expression (a).
  • TS (MPa) tensile breaking strength
  • the tensile strength at break of general polyethylene is as low as about 45 MPa even with the highest density polyethylene. Further, conventional ultra-high molecular weight polyethylene has not been able to make full use of its high molecular weight, and the tensile strength at break was equivalent to that of general polyethylene, and did not exceed 50 MPa. For this reason, a method has been adopted in which the strength is increased by orientation by rolling at a high draw ratio.
  • the ultra high molecular weight polyethylene particles have moderately entangled polymer chains, even when the [ ⁇ ] is in the region of ultra high molecular weight polyethylene exceeding 15 dl / g, preferably its molecular weight Even if it raises, tensile fracture strength does not fall, but rather shows the tendency to improve further. And, as the ultra high molecular weight polyethylene particles, the strength becomes more excellent when formed into a film. Therefore, if the ultra high molecular weight polyethylene particles belong to the high density polyethylene region, the tensile breaking strength measured by the above (4) is 40 MPa. It is preferable that it has the above, More preferably, it has 50 MPa or more.
  • the measurement conditions for the tensile strength at break are not particularly limited.
  • a strip or dumbbell test piece having a thickness of 0.1 to 5 mm and a width of 1 to 50 mm is used, and a tensile speed of 1 mm / min to 500 mm / min.
  • a method of measuring by speed can be exemplified.
  • the ultra high molecular weight polyethylene particles have a relatively low content of low molecular weight components, enable moderate entanglement of polymer chains, and become a stretched microporous film made of ultra high molecular weight polyethylene that is particularly excellent in heat resistance.
  • the fracture stress (MTS (MPa)) when the heat compression-molded sheet is melt-drawn at a temperature 20 ° C. higher than Tm 2 of the 2nd scan measured in (3) is 1.5 MPa or more. It is preferable that it has 2 MPa or more.
  • general polyethylene having a molecular weight of 500,000 or less has high fluidity at a temperature 20 ° C. higher than the melting point (Tm), and the molded body is deformed by its own weight, so that it cannot be melt-stretched.
  • the conventional ultrahigh molecular weight polyethylene can be melt-stretched even at a temperature 20 ° C. higher than the melting point (Tm), but strain hardening does not occur due to the low molecular weight component contained, and the stress remains low. In many cases, the fracture occurred due to a stress of about 1 MPa, resulting in poor heat resistance.
  • the molding conditions of the heat compression molded sheet used for melt drawing are not limited, for example, a press temperature of 100 to 250 ° C. and a press pressure of 5 to 50 MPa, and among them, the heat compression described in the above (4) is particularly preferable.
  • a molding method can be exemplified.
  • the melt stretching method include a method of stretching a test piece such as a strip or dumbbell having a thickness of 0.1 to 5 mm and a width of 1 to 50 mm at a tensile speed of 1 mm / min to 500 mm / min. be able to.
  • the ultrahigh molecular weight polyethylene particles become a stretched microporous film made of ultrahigh molecular weight polyethylene that is particularly excellent in heat resistance, (6) breaking stress (MTS (MPa)) when melt stretched as measured in (5) above
  • MTS breaking stress
  • the intrinsic viscosity ([ ⁇ ]) preferably satisfy the following relational expression (b), and particularly satisfy the following relational expression (d). It is preferable that MTS ⁇ 0.11 ⁇ [ ⁇ ] (b) 0.11 ⁇ [ ⁇ ] ⁇ MTS ⁇ 0.32 ⁇ [ ⁇ ] (d)
  • the ultra high molecular weight polyethylene particles are particularly excellent in fluidity as a powder, and become a stretched microporous film made of ultra high molecular weight polyethylene having excellent molding processability and physical properties.
  • the average particle diameter is 1 ⁇ m or more and 1000 ⁇ m or less. Are preferred.
  • the average particle size can be measured by a method such as a sieving test method using a standard sieve defined in JIS Z8801, for example
  • any method may be used as long as the ultra high molecular weight polyethylene particles can be produced.
  • a polyethylene production catalyst ethylene homopolymerization, ethylene and other
  • the method for copolymerizing with olefins include ⁇ -olefins such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. it can.
  • the polymerization method include a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, a slurry polymerization method, and the like.
  • ultra high molecular weight polyethylene particles having a particularly uniform particle shape is possible.
  • Ultra-high-molecular-weight polyethylene particles capable of providing a stretched microporous film made of ultra-high-molecular-weight polyethylene that has high melting point and high crystallinity, and excellent mechanical strength, heat resistance, and wear resistance It is preferable to use a slurry polymerization method because it can be produced in a simple manner.
  • the solvent used in the slurry polymerization method may be any organic solvent that is generally used, such as benzene, toluene, xylene, pentane, hexane, heptane, etc., and liquefied gas such as isobutane and propane, Olefins such as propylene, 1-butene, 1-octene and 1-hexene can also be used as a solvent.
  • organic solvent such as benzene, toluene, xylene, pentane, hexane, heptane, etc.
  • liquefied gas such as isobutane and propane
  • Olefins such as propylene, 1-butene, 1-octene and 1-hexene can also be used as a solvent.
  • any catalyst can be used as long as the ultra high molecular weight polyethylene particles can be produced.
  • transition metal compound (A) examples include a transition metal compound having a (substituted) cyclopentadienyl group and a (substituted) fluorenyl group, and a transition having a (substituted) cyclopentadienyl group and a (substituted) indenyl group.
  • Metal compounds, transition metal compounds having a (substituted) indenyl group and a (substituted) fluorenyl group, etc. can be mentioned. Examples of the transition metal in this case include zirconium, hafnium, etc.
  • a zirconium compound having a (substituted) cyclopentadienyl group and an amino group-substituted fluorenyl group a (substituted) cyclopentadienyl group and an amino group-substituted fluorenyl group It is preferable that it is a hafnium compound.
  • diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride diphenylmethylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride
  • diphenyl Methylene (4-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride
  • diphenylsilanediyl (cyclopentadienyl) (2- (dimethylamino) -9-fluorenyl) zirconium Dichloride diphenylsilanediyl (cyclopentadienyl) (2- (diethylamino) -9-fluorenyl) zirconium dichloride
  • Examples of the organically modified clay (B) modified with the aliphatic salt include N, N-dimethyl-behenylamine hydrochloride, N-methyl-N-ethyl-behenylamine hydrochloride, N-methyl-Nn- Propyl-behenylamine hydrochloride, N, N-dioleyl-methylamine hydrochloride, N, N-dimethyl-behenylamine hydrofluoride, N-methyl-N-ethyl-behenylamine hydrofluoride, N- Methyl-Nn-propyl-behenylamine hydrofluoride, N, N-dioleyl-methylamine hydrofluoride, N, N-dimethyl-behenylamine hydrobromide, N-methyl-N— Ethyl-behenylamine hydrobromide, N-methyl-Nn-propyl-behenylamine hydrobromide, N, N-dioleyl-methylamine hydrobromide, N
  • the clay compound constituting the organically modified clay (B) may be any clay compound as long as it belongs to the category of clay compounds, and generally a tetrahedron in which a silica tetrahedron is two-dimensionally continuous.
  • a layer called a silicate layer formed by combining a sheet and an octahedron sheet in which an alumina octahedron, a magnesia octahedron, etc. are two-dimensionally continuous in a 1: 1 or 2: 1 layer is formed to overlap.
  • silica tetrahedrons are replaced with the same type of Si by Al, alumina octahedron Al by Mg, magnesia octahedron Mg by Li, etc. It is known that cations such as Na + and Ca 2+ exist between the layers in order to compensate for this negative charge.
  • the clay compound kaolinite, talc, smectite, vermiculite, mica, brittle mica, curdstone and the like as natural products or synthetic products exist, and these can be used. Smectite is preferable from the viewpoint of easiness of modification and organic modification, and hectorite or montmorillonite is more preferable among smectites.
  • the organically modified clay (B) can be obtained by introducing the aliphatic salt between layers of the clay compound to form an ionic complex.
  • it is preferable to carry out the treatment by selecting the conditions of a clay compound concentration of 0.1 to 30% by weight and a treatment temperature of 0 to 150 ° C.
  • the aliphatic salt may be prepared as a solid and dissolved in a solvent for use, or a solution of the aliphatic salt may be prepared by a chemical reaction in the solvent and used as it is.
  • the reaction amount ratio between the clay compound and the aliphatic salt it is preferable to use an aliphatic salt having an equivalent amount or more with respect to exchangeable cations of the clay compound.
  • processing solvent examples include aliphatic hydrocarbons such as pentane, hexane, and heptane; aromatic hydrocarbons such as benzene and toluene; alcohols such as ethyl alcohol and methyl alcohol; ethers such as ethyl ether and n-butyl ether.
  • Halogenated hydrocarbons such as methylene chloride and chloroform; acetone; 1,4-dioxane; tetrahydrofuran; water;
  • alcohols or water is used alone or as one component of a solvent.
  • the particle diameter of the organically modified clay (B) constituting the polyethylene production catalyst is not limited, and among them, the efficiency during catalyst preparation and the efficiency during polyethylene production are excellent. preferable. There is no limitation on the method of adjusting the particle size at that time, and large particles may be pulverized to an appropriate particle size, small particles may be granulated to an appropriate particle size, or pulverization and granulation May be combined. The particle size may be adjusted on the clay before organic modification or on the organic modified clay after modification.
  • organoaluminum compound (C) may be used as long as it belongs to the category called organoaluminum compound, and examples thereof include alkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum. Can do.
  • the transition metal compound (A) (hereinafter also referred to as component (A)) constituting the catalyst for producing polyethylene, the organically modified clay (B) (hereinafter also referred to as component (B)), and
  • any method may be used as long as it is possible to prepare the polyethylene production catalyst containing the component (A), the component (B) and the component (C).
  • a method in which each of the components (A), (B) and (C) is mixed in an inert solvent or using a monomer for polymerization as a solvent there is no restriction
  • the polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration when producing the ultrahigh molecular weight polyethylene particles can be arbitrarily selected.
  • the polymerization temperature is 0 to 100 ° C.
  • the polymerization time is 10 seconds to
  • the polymerization is preferably carried out for 20 hours in the range of normal polymerization pressure to 100 MPa. It is also possible to adjust the molecular weight using hydrogen during polymerization.
  • the polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions.
  • the polyethylene particles obtained after the completion of the polymerization can be obtained by separating and recovering from the polymerization solvent by a conventionally known method and drying.
  • the stretched microporous membrane made of ultrahigh molecular weight polyethylene of the present invention may be composed of an ultrahigh molecular weight polyethylene composition containing ultrahigh molecular weight polyethylene having [ ⁇ ] of 7 dl / g or more and 60 dl / g or less.
  • Composition with polyethylene because it has excellent heat resistance, durability at high temperatures, and thin film properties, as well as emergency shutdown when applied as a battery separator such as a lithium ion secondary battery.
  • it is preferably made of a composition with polyethylene having a weight average molecular weight of 800,000 or less.
  • general commercially available polyethylene may be sufficient.
  • the ultra high molecular weight polyethylene composition in which [ ⁇ ] of the ultra high molecular weight polyethylene composition is 0.75 times or less of [ ⁇ ] of the ultra high molecular weight polyethylene component. It is preferable.
  • the temperature is increased from 0 ° C. to 230 ° C. at a temperature increase rate of 10 ° C./min by DSC. among the endothermic peak due to melting of upon, ⁇ H whole (J / g) than 135 ° C. for ⁇ H> 135 (J / g) of occupying ratio ( ⁇ H> 135 / ⁇ H whole) 80% or less 40% or more, and An ultrahigh molecular weight polyethylene stretched microporous membrane exhibiting a ⁇ H whole of 190 J / g or more is preferred.
  • the temperature is increased from 0 ° C.
  • the heat flux at the maximum temperature is in the range of 134 ° C. or lower and 140 ° C. or higher.
  • the ultra-high molecular weight polyethylene stretched microporous membrane of the present invention preferably has a thickness of 0.001 to 1 mm and an average pore diameter of 1 to 1000 nm.
  • the film thickness (mm) of the stretched microporous film in the present invention can be obtained as an average value by measuring the film thickness with a contact-type film thickness meter at, for example, 30 points of the stretched microporous film.
  • the average pore diameter can be obtained by image analysis from an image obtained by observation with a scanning electron microscope in addition to the nitrogen adsorption method and the mercury intrusion method.
  • the stretched microporous curtain made of ultrahigh molecular weight polyethylene of the present invention preferably has a stretch ratio of 2 to 20 times in the longitudinal direction and 2 to 20 times in the transverse direction.
  • the method for producing the stretched microporous membrane made of ultrahigh molecular weight polyethylene of the present invention is not particularly limited.
  • ultrahigh molecular weight polyethylene, the ultrahigh molecular weight polyethylene particles, the ultrahigh molecular weight polyethylene composition and an organic solvent are mixed at 50 ° C. or higher and 300 ° C.
  • a method of adding a step of removing the organic solvent from the sheet-like material and a step of biaxial stretching after mixing at a temperature of 0 ° C. or less to obtain a sheet-like material can be mentioned.
  • organic solvent used here examples include aliphatic hydrocarbons or alicyclic hydrocarbons having a high boiling point such as octane, decane, dodecane, octadencan, decahydronaphthalene, and tetrahydronaphthalene; aromatics such as benzene, toluene, xylene, and naphthalene.
  • Hydrocarbons Halogenated hydrocarbons such as dichloroethane, trichloroethane, chlorobenzene, and trichlorobenzene; linear or branched liquid paraffin; paraffin wax; higher alcohols having 5 or more carbon atoms; phthalates, or mixtures thereof Can do.
  • the ultrahigh molecular weight polyethylene, the ultrahigh molecular weight polyethylene particles, or the ultrahigh molecular weight polyethylene composition and an organic solvent are mixed, a stretched microporous membrane excellent in uniformity and smoothness can be obtained efficiently.
  • the ultra high molecular weight polyethylene particles, or the ultra high molecular weight polyethylene composition preferably has a concentration of 0.5 wt% or more and 60 wt% or less, particularly preferably 5 wt% or more and 40 wt% or less.
  • the ultrahigh molecular weight polyethylene, the ultrahigh molecular weight polyethylene particles, or the ultrahigh molecular weight polyethylene composition and the organic solvent are mixed, for example, a method of mixing in a reaction vessel equipped with a stirring blade, a single shaft, two Examples thereof include a method of extrusion kneading with an extruder such as a shaft, and a method of extrusion kneading after mixing in a reactor.
  • the obtained mixture is shape
  • the step of removing the organic solvent from the sheet-like material for example, a drying method by heating, a method of drying after solvent extraction with a low melting point aliphatic or alicyclic hydrocarbon, alcohol, halogenated hydrocarbon, etc.
  • the biaxial stretching step include a simultaneous biaxial stretching method and a sequential biaxial stretching method in which sequential biaxial stretching is performed, and the stretching speed and stretching temperature at that time are constant. Alternatively, it may be multi-stage with change.
  • the stretching temperature is preferably 0 ° C. or higher and 200 ° C. or lower.
  • the order of the organic solvent removal step and the biaxial stretching step is arbitrary.
  • the biaxial stretching may be performed after the organic solvent is removed, or the organic solvent may be removed after the biaxial stretching. These may be performed simultaneously.
  • annealing can also be given after extending
  • the stretched microporous membrane made of ultrahigh molecular weight polyethylene has a heat stabilizer, a weather stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a slip agent, a lubricant, and a nucleus as long as it does not depart from the object of the present invention
  • Agents, pigments, etc . inorganic fillers or reinforcing agents such as carbon black, talc, glass powder, glass fiber, metal powder; organic fillers or reinforcing agents; flame retardants; known additives such as neutron shielding agents; High density polyethylene (HDPE), linear low density polyethylene (L-LDPE), low density polyethylene (LDPE), polypropylene resin, poly-1-butene, poly-4-methyl-1-pentene, ethylene / vinyl acetate
  • a resin such as a copolymer, an ethylene / vinyl alcohol copolymer, polystyrene, or a maleic anhydride graft thereof may be blended.
  • ultra high molecular weight polyethylene As the method of adding the agent, ultra high molecular weight polyethylene, a method of blending with the ultra high molecular weight polyethylene particles, ultra high molecular weight polyethylene, a method of blending with the ultra high molecular weight polyethylene particles at the time of molding, dry blending or melt blending in advance And the like.
  • the stretched microporous membrane made of ultra high molecular weight polyethylene of the present invention is excellent in strength and heat resistance, gas separation membrane, gas permeable membrane, tape, tube, lead storage battery, nickel metal hydride battery, lithium battery, lithium ion secondary battery It can be used as a member such as a battery separator.
  • the ultra-high molecular weight polyethylene stretched microporous membrane of the present invention is excellent in heat resistance, durability at high temperatures, and stability, and when applied as a separator of a lithium ion secondary battery, it is small and light by thinning. It is not only easy to use, but also has excellent shutdown performance and safety in an emergency, making it particularly suitable. And when using the extending
  • the positive electrode can include a lithium metal oxide, such as cobalt-manganese-nickel composite oxide-lithium, and the cathode can include a carbon material, such as graphite.
  • the electrolytic solution may include an ethyl carbonate / diethyl carbonate solution of 1M LiPF 6 .
  • the stretched microporous membrane made of ultra high molecular weight polyethylene obtained by the present invention is excellent in strength, heat resistance, durability at high temperature, and thinning, so that it is a gas separation membrane, gas permeable membrane, tape, tube, lead acid battery, nickel It is suitably used for battery separators such as hydrogen batteries, lithium batteries, and lithium ion secondary batteries.
  • a jet mill manufactured by Seishin Enterprise Co., Ltd., (trade name) CO-JET SYSTEM ⁇ MARK III was used. (Trade name) MT3000) was used to measure ethanol as a dispersant.
  • Tm 1 and Tm 2 ⁇ Measurement of Tm 1 and Tm 2 ⁇ Using DSC (product name: DSC6220, manufactured by SII NanoTechnology Co., Ltd.), the 1st scan was performed at a heating rate of 10 ° C./min, and the crystal melting peak (Tm 1 ) of the 1st scan was measured. Thereafter, after standing for 5 minutes, the temperature was lowered to ⁇ 20 ° C. at a rate of temperature drop of 10 ° C./min. After standing for 5 minutes, the 2nd scan was performed again to measure the 2nd scan crystal melting peak (Tm 2 ). In this case, the sample amount of ultra high molecular weight polyethylene was 4 to 6 mg.
  • DSC product name: DSC6220, manufactured by SII NanoTechnology Co., Ltd.
  • DSC6220 manufactured by SII NanoTechnology Co., Ltd.
  • the heat flux at the temperature at which the bundle is maximum and the heat flux at the temperature at which the heat flux at the endotherm is maximum at 140 ° C. or higher were determined, and the respective ratios were determined.
  • the ultra high molecular weight polyethylene was incinerated, alkali melted, and the prepared solution was used to determine the titanium content in the ultra high molecular weight polyethylene using an ICP emission analyzer (manufactured by PerkinElmer Co., Ltd., (trade name) Optima 3000XL). It was measured.
  • the evaluation sheet for ultrahigh molecular weight polyethylene particles was molded by the following method. That is, ultra high molecular weight polyethylene particles were sandwiched between polyethylene terephthalate films, preheated at 190 ° C. for 5 minutes, and then heat-rolled under conditions of 190 ° C. and a press pressure of 20 MPa. Thereafter, the mold was cooled at a mold temperature of 110 ° C. for 10 minutes to prepare a press sheet having a thickness of 0.3 mm.
  • the film thickness (d, mm) of the microporous film was determined by measuring the film thickness with a contact-type film thickness meter at 30 points of the microporous film, and taking the average value.
  • the porosity (V,%) was calculated by measuring the weight (W, g) of a 10 cm ⁇ 10 cm microporous membrane, and calculating the true density (0.950 g / cm 3 ) of the porous membrane as shown below (e).
  • V 100 ⁇ W / 0.095d (e) -Measurement of pore distribution in stretched microporous membrane- After gold deposition, the surface of the microporous film was observed with a scanning electron microscope (manufactured by Keyence Co., Ltd., (trade name) VE-9800) at a magnification of 10,000 times, and the obtained SEM photograph was analyzed by image analysis. The pore distribution was obtained, approximated to a geometric logarithmic distribution function, and the median diameter was taken as the average pore diameter.
  • the heat shrinkage rate was calculated by calculating the rate of change in length and width after heating a 5 cm ⁇ 5 cm microporous membrane at 100 ° C. for 1 hour and allowing it to cool at room temperature for 24 hours.
  • the secondary battery was discharged for 10 seconds at a constant current corresponding to 2C (current value at which the discharge capacity of the lithium ion secondary battery was discharged at 0.5 hour).
  • the voltage rise at that time was measured, and the DC resistance value was calculated from the current value dependence (IR loss) of this voltage drop.
  • the measurement temperature is 25 ° C.
  • the slurry was separated by filtration, washed twice with 600 ml of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 160 g of organically modified clay.
  • This organically modified clay was pulverized by a jet mill to have a median diameter of 7 ⁇ m.
  • Production Example 2 (1) Preparation of organically modified clay The same procedure as in Production Example 1 was performed.
  • Production Example 3 (1) Preparation of organically modified clay A 1-liter flask was charged with 300 ml of industrial alcohol (product name: Echinen F-3, manufactured by Nippon Alcohol Sales) and 300 ml of distilled water, and 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion After adding 42.4 g (120 mmol) of (trade name) Armin DM22D manufactured by Co., Ltd. and heating to 45 ° C., 100 g of synthetic hectorite (Rockwood Additives, (trade name) Laponite RDS) was dispersed. The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature.
  • industrial alcohol product name: Echinen F-3, manufactured by Nippon Alcohol Sales
  • 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine Lion After adding 42.4 g (120 mmol) of (trade name) Armin DM22D manufactured by Co., Ltd. and heating to 45 ° C.,
  • the slurry was separated by filtration, washed twice with 600 ml of 60 ° C. water, and dried in an oven at 85 ° C. for 12 hours to obtain 125 g of an organically modified clay.
  • This organically modified clay was pulverized by a jet mill to have a median diameter of 7 ⁇ m.
  • Production Example 4 (1) Preparation of solid catalyst component In a 1 liter glass flask equipped with a thermometer and a reflux tube, 50 g (2.1 mol) of metal magnesium powder and 210 g (0.62 mol) of titanium tetrabutoxide were added. Then, 320 g (4.3 mol) of n-butanol in which 0.5 g was dissolved was added at 90 ° C. over 2 hours, and further stirred at 140 ° C. for 2 hours under a nitrogen seal while excluding generated hydrogen gas to obtain a homogeneous solution. . Then 2100 ml of hexane was added.
  • Production Example 5 (1) Preparation of organically modified clay and (2) Preparation of suspension of catalyst for polyethylene production were carried out in the same manner as in Production Example 2.
  • Production Example 6 (1) Preparation of organically modified clay and (2) Preparation of suspension of catalyst for polyethylene production were carried out in the same manner as in Production Example 2.
  • Production Example 7 (1) The solid catalyst component was prepared in the same manner as in Production Example 4.
  • Production Example 8 (1) The solid catalyst component was prepared in the same manner as in Production Example 4.
  • Example 1 In a 500 ml glass flask, 14 g of ultra high molecular weight polyethylene particles (1) produced in Production Example 1 and 56 g of liquid paraffin (manufactured by Wako Pure Chemicals, special grade), (trade name) Irganox 1010 (manufactured by BASF) 0. 13 g and (trade name) Irgafos 168 (manufactured by BASF) 0.13 g were heated and mixed at 150 ° C. for 1 hour.
  • liquid paraffin manufactured by Wako Pure Chemicals, special grade
  • Irganox 1010 manufactured by BASF
  • BASF liquid paraffin
  • Irgafos 168 manufactured by BASF
  • the obtained mixture was kneaded with a 100 cc batch kneader (trade name: Laboplast Mill 4C150, manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a kneading temperature of 190 ° C. and a rotation speed of 50 rpm for 10 minutes.
  • a 100 cc batch kneader (trade name: Laboplast Mill 4C150, manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a kneading temperature of 190 ° C. and a rotation speed of 50 rpm for 10 minutes.
  • This sheet-like material is simultaneously biaxially stretched at 115 ° C. so that the set stretching ratio is 4 ⁇ 4 times in the longitudinal direction ⁇ lateral direction, washed with hexane, liquid paraffin is removed, and dried. Thus, a stretched microporous membrane was produced.
  • the obtained stretched microporous membrane had no holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope.
  • Table 2 shows the film thickness, porosity, tensile rupture strength, and rupture stress during melt drawing of this stretched microporous membrane.
  • Comparative Example 1 A microporous membrane was produced in the same manner as in Example 1 except that the ultrahigh molecular weight polyethylene (4) produced in Production Example 4 was used instead of the ultrahigh molecular weight polyethylene particles (1).
  • the obtained film had no holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope.
  • Table 2 shows the film thickness, porosity, tensile strength at break, and breaking stress at the time of melt stretching. It was inferior in tensile strength at break, particularly heat resistance.
  • Comparative Example 2 Example 1 except that (trade name) Million 240M (manufactured by Mitsui Chemicals, Inc.) (hereinafter referred to as ultra high molecular weight polyethylene (5)) was used in place of the ultra high molecular weight polyethylene particles (1).
  • a microporous membrane was produced by the same method.
  • the obtained film had no holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope.
  • Table 2 shows the film thickness, porosity, tensile strength at break, and breaking stress at the time of melt stretching. It was inferior in tensile strength at break, particularly heat resistance.
  • Example 2 A stretched microporous membrane made of ultrahigh molecular weight polyethylene was prepared in the same manner as in Example 1 except that the ultrahigh molecular weight polyethylene particles (2) produced in Production Example 2 were used instead of the ultrahigh molecular weight polyethylene particles (1). Manufactured.
  • the obtained stretched microporous membrane had no holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope.
  • Table 2 shows the film thickness, porosity, tensile rupture strength, and rupture stress during melt drawing of this stretched microporous membrane.
  • Example 3 Except that the thickness of the sheet of the mixture was 0.9 mm, the set stretching ratio was 5 ⁇ 5 times in the longitudinal direction ⁇ lateral direction, and the stretching temperature was 110 ° C. A stretched microporous membrane made of molecular weight polyethylene was produced.
  • the obtained stretched microporous film had no holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope.
  • Table 2 shows the film thickness, porosity, tensile rupture strength, and rupture stress during melt drawing of this stretched microporous membrane.
  • Example 4 A stretched microporous membrane made of ultrahigh molecular weight polyethylene was prepared in the same manner as in Example 1 except that the ultrahigh molecular weight polyethylene particles (3) produced in Production Example 3 were used instead of the ultrahigh molecular weight polyethylene particles (1). Manufactured.
  • the obtained stretched porous film had no holes or tears that could be confirmed with the naked eye, and microscopic pores were observed with an electron microscope.
  • Table 2 shows the film thickness, porosity, tensile rupture strength, and rupture stress during melt drawing of this stretched microporous membrane.
  • Example 5 instead of 14g of ultra high molecular weight polyethylene particles (1) and 56g of liquid paraffin (made by Wako Pure Chemicals, special grade), 17.5g of ultra high molecular weight polyethylene particles (1) and liquid paraffin (made by MORESCO, (trade name) Moresco) White P-350P) A sheet-like material having a thickness of 0.9 mm obtained in the same manner as in Example 1 except that 52.5 g was used, and the set stretching ratio was 6 ⁇ 6 times in the longitudinal direction ⁇ lateral direction. Thus, a stretched microporous membrane having a thickness of 14 ⁇ m was produced by sequentially biaxially stretching at 115 ° C., washing with methylene chloride, removing liquid paraffin, and drying.
  • the obtained stretched microporous membrane did not have holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope. Measurement results of the stretched microporous film thickness, porosity, average pore diameter, tensile breaking strength, breaking stress during melt drawing, DSC melting heat ( ⁇ H whole , ⁇ H > 135 ), and application to lithium ion secondary batteries Table 2 shows the measurement results of DC resistance and charge / discharge efficiency.
  • Example 6 instead of the ultrahigh molecular weight polyethylene particles (1), the ultrahigh molecular weight polyethylene particles (2) produced in Production Example 2 were used. A stretched microporous membrane was produced.
  • the obtained stretched microporous membrane did not have holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope. Measurement results of the stretched microporous film thickness, porosity, average pore diameter, tensile breaking strength, breaking stress during melt drawing, DSC melting heat ( ⁇ H whole , ⁇ H > 135 ), and application to lithium ion secondary batteries Table 2 shows the measurement results of DC resistance and charge / discharge efficiency.
  • Example 7 Instead of the ultrahigh molecular weight polyethylene particles (1), the ultrahigh molecular weight polyethylene particles (6) produced in Production Example 5 are used, and the set stretching ratio is 5.5 times x 6.5 times in the machine direction x transverse direction. A stretched microporous membrane made of ultrahigh molecular weight polyethylene having a thickness of 14 ⁇ m was produced in the same manner as in Example 5 except that stretching was performed as described above.
  • the obtained stretched microporous membrane did not have holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope. Measurement results of the stretched microporous film thickness, porosity, average pore diameter, tensile breaking strength, breaking stress during melt drawing, DSC melting heat ( ⁇ H whole , ⁇ H > 135 ), and application to lithium ion secondary batteries Table 2 shows the measurement results of DC resistance and charge / discharge efficiency.
  • Example 8 Instead of 14 g of ultra high molecular weight polyethylene particles (1) and 56 g of liquid paraffin (manufactured by Wako Pure Chemicals, special grade), 6.3 g of ultra high molecular weight polyethylene particles (1) produced in Production Example 1 and weight produced in Production Example 7 A thickness of 0 obtained in the same manner as in Example 1 except that 14.7 g of polyethylene having an average molecular weight of 51 ⁇ 10 4 and 49 g of liquid paraffin (manufactured by MORESCO, (trade name) Moresco White P-350P) were used. .9 mm sheet-like material is simultaneously biaxially stretched at 115 ° C. so that the set stretching ratio is 6 ⁇ 6 times in the machine direction ⁇ horizontal direction, washed with hexane, liquid paraffin is removed, and dried. Thus, a stretched microporous film having a film thickness of 12 ⁇ m was produced.
  • the obtained stretched microporous membrane did not have holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope.
  • the temperature at which the flux is the highest and the ratio of the heat flux at that time to the maximum heat flux in the range of 140 ° C or higher, the temperature at which the heat flux is the highest and the ratio of the heat flux at that time to the maximum heat flux, tensile fracture strength, heat shrinkage Table 3 shows the measurement results of the rate, the breaking stress at the time of melt drawing, and the measurement results of the DC resistance and the charge / discharge efficiency when applied to the lithium ion secondary battery.
  • Comparative Example 3 In place of 6.3 g of the ultrahigh molecular weight polyethylene particles (1) produced in Production Example 1 and 14.7 g of polyethylene having a weight average molecular weight of 51 ⁇ 10 4 , the ultrahigh molecular weight polyethylene particles (4) produced in Production Example 4 were used.
  • a stretched microporous membrane was produced in the same manner as in Example 8, except that 3 g and 14.7 g of polyethylene having a weight average molecular weight of 51 ⁇ 10 4 produced in Production Example 7 were used.
  • the obtained stretched microporous membrane did not have holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope.
  • the endotherm above 140 ° C was not measured.
  • the tensile fracture strength was low, the heat shrinkage rate was high, and the DC resistance and charge / discharge efficiency when applied to a lithium ion secondary battery were also inferior.
  • Example 9 Ultra high molecular weight polyethylene particles (2) produced in Production Example 2 instead of 6.3 g of ultra high molecular weight polyethylene particles (1) produced in Production Example 1 and 14.7 g of polyethylene having a weight average molecular weight of 51 ⁇ 10 4 .
  • a stretched microporous membrane having a film thickness of 13 ⁇ m was produced in the same manner as in Example 8 except that 3 g and 15.7 g of polyethylene having a weight average molecular weight of 51 ⁇ 10 4 produced in Production Example 7 were used.
  • the obtained stretched microporous membrane did not have holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope.
  • the temperature at which the flux is the highest and the ratio of the heat flux at that time to the maximum heat flux in the range of 140 ° C or higher, the temperature at which the heat flux is the highest and the ratio of the heat flux at that time to the maximum heat flux, tensile fracture strength, heat shrinkage Table 3 shows the measurement results of the rate, the breaking stress at the time of melt drawing, and the measurement results of the DC resistance and the charge / discharge efficiency when applied to the lithium ion secondary battery.
  • Example 10 Instead of 6.3 g of the ultrahigh molecular weight polyethylene particles (1) produced in Production Example 1 and 14.7 g of polyethylene having a weight average molecular weight of 51 ⁇ 10 4 , the ultrahigh molecular weight polyethylene particles (2) produced in Production Example 2 were used. A stretched microporous membrane having a thickness of 13 ⁇ m was produced in the same manner as in Example 8, except that 3 g and 14.7 g of polyethylene having a weight average molecular weight of 32.1 ⁇ 10 4 produced in Production Example 8 were used.
  • the obtained stretched microporous membrane did not have holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope.
  • the temperature at which the flux is the highest and the ratio of the heat flux at that time to the maximum heat flux in the range of 140 ° C or higher, the temperature at which the heat flux is the highest and the ratio of the heat flux at that time to the maximum heat flux, tensile fracture strength, heat shrinkage Table 3 shows the measurement results of the rate, the breaking stress at the time of melt drawing, and the measurement results of the DC resistance and the charge / discharge efficiency when applied to the lithium ion secondary battery.
  • Example 11 The ultra high molecular weight polyethylene particles (3) produced in Production Example 3 instead of 6.3 g of the ultra high molecular weight polyethylene particles (1) produced in Production Example 1 and 14.7 g of polyethylene having a weight average molecular weight of 51 ⁇ 10 4 .
  • a stretched microporous membrane having a thickness of 12 ⁇ m was produced in the same manner as in Example 8, except that 27.8 g of polyethylene having a weight average molecular weight of 51 ⁇ 10 4 produced in Production Example 7 was used.
  • the obtained stretched microporous membrane did not have holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope.
  • the temperature at which the flux is the highest and the ratio of the heat flux at that time to the maximum heat flux in the range of 140 ° C or higher, the temperature at which the heat flux is the highest and the ratio of the heat flux at that time to the maximum heat flux, tensile fracture strength, heat shrinkage Table 3 shows the measurement results of the rate, the breaking stress at the time of melt drawing, and the measurement results of the DC resistance and the charge / discharge efficiency when applied to the lithium ion secondary battery.
  • Example 12 Ultra high molecular weight polyethylene particles (6) produced in Production Example 5 instead of 6.3 g of ultra high molecular weight polyethylene particles (1) produced in Production Example 1 and 14.7 g of polyethylene having a weight average molecular weight of 51 ⁇ 10 4 .
  • a stretched microporous membrane having a film thickness of 13 ⁇ m was produced in the same manner as in Example 8, except that 4 g and 12.6 g of polyethylene having a weight average molecular weight of 51 ⁇ 10 4 produced in Production Example 7 were used.
  • the obtained stretched microporous membrane did not have holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope.
  • the temperature at which the flux is the highest and the ratio of the heat flux at that time to the maximum heat flux in the range of 140 ° C or higher, the temperature at which the heat flux is the highest and the ratio of the heat flux at that time to the maximum heat flux, tensile fracture strength, heat shrinkage Table 3 shows the measurement results of the rate, the breaking stress at the time of melt drawing, and the measurement results of the DC resistance and the charge / discharge efficiency when applied to the lithium ion secondary battery.
  • Example 13 The ultra high molecular weight polyethylene particles (1) produced in Production Example 1 and the weight produced in Production Example 8 instead of the ultra high molecular weight polyethylene particles (7) produced in Production Example 6 instead of the polyethylene having a weight average molecular weight of 52 ⁇ 10 4
  • a stretched microporous membrane having a thickness of 13 ⁇ m was produced in the same manner as in Example 8 except that polyethylene having an average molecular weight of 32.1 ⁇ 10 4 was used.
  • the obtained stretched microporous membrane did not have holes or tears that could be confirmed with the naked eye, and micropores were observed with an electron microscope.
  • the temperature at which the flux is the highest and the ratio of the heat flux at that time to the maximum heat flux in the range of 140 ° C or higher, the temperature at which the heat flux is the highest and the ratio of the heat flux at that time to the maximum heat flux, tensile fracture strength, heat shrinkage Table 3 shows the measurement results of the rate, the breaking stress at the time of melt drawing, and the measurement results of the DC resistance and the charge / discharge efficiency when applied to the lithium ion secondary battery.
  • the stretched microporous membrane made of ultra high molecular weight polyethylene obtained by the present invention is excellent in strength, heat resistance, durability at high temperature, and thinning, so that it is a gas separation membrane, gas permeable membrane, tape, tube, lead acid battery, nickel Lithium ion secondary battery that can be used in various applications such as battery separators such as hydrogen batteries, lithium batteries, lithium ion secondary batteries, etc., and has excellent electrical characteristics especially when applied as a separator for lithium ion secondary batteries Can be provided.

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  • Polymers & Plastics (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Cell Separators (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un film poreux étiré de polyéthylène de poids moléculaire ultra-élevé présentant une résistance et une thermorésistance élevées. L'invention concerne un film poreux étiré de polyéthylène de poids moléculaire ultra-élevé, comprenant au moins un polyéthylène de poids moléculaire ultra-élevé avec une viscosité inhérente ([η]) de 7 à 60 dl/g inclus et présentant une porosité de 10 à 70 % inclus et une contrainte à la rupture d'au moins 1 MPa lorsqu'il est étiré à l'état fondu à 150 °C. Pour le polyéthylène de poids moléculaire ultra-élevé, il est préférable d'utiliser des particules de polyéthylène de poids moléculaire ultra-élevé qui satisfont : (1) une viscosité inhérente ([η]) de 7 à 60 dl/g inclus, (2) une densité en vrac de 130 à 700 kg/m3, et (3) une ΔTm (ΔTm = Tm1 − Tm2) qui est la différence entre le point de fusion ((Tm1) sur un premier balayage et le point de fusion ((Tm2) sur un second balayage tel que mesuré par calorimétrie différentielle à balayage (DSC) de 9 à 30 °C inclus.
PCT/JP2015/058003 2014-03-26 2015-03-18 Film poreux étiré de polyéthylène de poids moléculaire ultra-élevé WO2015146733A1 (fr)

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KR1020167025631A KR102330629B1 (ko) 2014-03-26 2015-03-18 초고분자량 폴리에틸렌제 연신 미다공막

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